Washing agents containing optical brightening agents



United States Patent ice 3,392,122

Patented July 9, 1968 3 392 122 pounds of them have such a defect as to decrease the de- WASHING AGENTS CNTAIN-ING OPTICAL gree of whiteness in appearance of soaps and synthetic BRIGHTENING AGENTS Washington agents by the effects of external conditions Kenro Obayashi, Toyonaka-shi, Koichiro Ishihara, Nishisuch as moisture. The present inventors have solved these norniya-shi, Yuji Minagawa, Iked'a-shi, and Tomiro 5 problems. Noda, 053143, 1 35ign0fS sllmitflmo Chelmcal One object of the present invention is to provide soaps g pf i Hlgashl'kib Osaka, p a 'P and synthetic washing agents which are extremely imion 0 apan N0 Drawing. Filed Feb. 24 1965, Ser. No 435,021 pror ed in their whiteness 1n the appearance. Another ob ject is to provide soaps and synthetic washing agents hav- 4 4 Clams pnonty g f fg f Feb 2 196 mg high commercial value 1n their appearance. Another 11 Claims. (61. 252-152) object is to provide improved soaps and synthetic wash- The present invention relates to washing agents coning having P oPtical brightenmg abllity E taining optical brightening agents, more particularly it n as ullpmved Whlteness 111 appeijlrances- E f relates to Washing agents having improved White appear Ob ects will be apparent from the following descriptions. ance 15 In order to accomplish these objects the present inven- The washing agents according to the present invention tion provides Washing agents containing as a brightening include soaps and synthetic washing agents. agent a 4,4-bis-triazinyl-stilbene-2,2-disulfonic acid de- Soaps and synthetic washing agents are colored in pale rivative having the general formula,

IIQI N N l N N X2 soot 303M C C i {'2 yellow shade as their essential property, and due to these wherein X and X each represent a member selected facts their commercial value is very much decreased. from the group consisting of methyl and ethyl radicals, In other words, yellow colored soaps or synthetic wash- Y and Y each represent a member selected from the ing agents are not preferred by the customers and theregroup consisting of amino radical, aliphatic cyclic amine fore such colored soaps or synthetic washing agents are residues, primary and secondary alkyl amine residues, inferior in commercial value. Accordingly the improveprimary and secondary hydroxy alkylamine residues, ment of the appearance of the soaps and synthetic washprimary and secondary aromatic amine residues including ing agents, in other words to provide soaps and synthetic their nucleus substituted compounds, and alkoxy radicals,

washing agents having improved white appearance have and M represents a member selected from the group conbeen desired. sisting of hydrogen atom and alkali metals.

In order to satisfy such desire, various attempts have The compounds used in the present invention and repbeen carried t, resented by the above general formula, are produced by For example, soaps and synthetic washing agents conthe known method, by condensing in arbitrary order taining optical brightening agent have been proposed, in 1 mole portion of 4,4-diaminostilbene-2,2-disulfonic this case there was intended to give them the ability of acid, 2 mole portions of a cyanuric halide, 2 mole porbrightening action to the articles to be washed together tions of N-methylaniline or N-ethylaniline or a mixture with to improve the appearances of them. However, the of them, and 2 mole portions of at least one member proposed soaps and synthetic washing agents containing of the components corresponding to Y and Y in the conventional optical brightening agents have increased in above general formula. As the cyanuric halide, cyanuric yellow coloring rather than being improved in the white chloride, cyanuric bromide and cyanuric iodide may be appearance. In other words, the appearances of the conutilized, and among those cyanuric chloride is the most ventional soaps and washing agents containing convenpreferable from commercial point of view. In the above tional optical brightening agents have been unsatisfactory general formula, Y and Y each represent a member sein the commercial point of view, because of their pale lected from the group consisting of amino radical, aliphayellow colorings. tic cyclic amine residues, primary and secondary alkyl- For example, water soluble benzothiophene derivatives amine residues, primary and secondary hydroxyalkyldisclosed in the specification of Japanese Patent Publicaamine residues, primary and secondary aromatic amine tion Number SHO 27/4,339, fluorescent triazole comresidues including their nucleus substituted compounds, pounds disclosed in the specification of Japanese Patent and alkoxy radicals, in which examples of aliphatic cyclic Publication Number SHO 3 1/ 3,536 and others, and 4,4- amine include cyclohexylamine and morpholine, examples diaminostilbene-2,2-disulfonic acid derivatives containing of primary and secondary alkyl amine include monoacylamino group disclosed in the specification of Japanese methylarnine, monoethylamine, n-butylamine, dimethyl- Patent Publication Number SHO 30/7,061, are proposed amine, diethylarnine and methylethylamine, which have to be added to soaps and synthetic Washing agents in order 1-4 carbon atoms, examples of primary and secondary to improve the appearances of them as well as to give them hydroxyalkylamine include monoethanolamine, monoisothe optical brightening ability. However these proposals propanolamine, diethanolamine, methylethanolamine, are not yet satisfactory in the improvement of the appearethylethanolamine and diisopropanolamine, which have ances of soaps and synthetic Washing agents, nor in the im- 13 carbon atoms in each alkyl radical, examples of provement of their optical brightening action to the primary and secondary aromatic amine including their articles to be washed. nucleus substituted compound include aniline, toluidines,

Further, 4,4-bis-triazinylamino stilbene-2,2-disulfonic chloroanilines, aniline sulfonic acids such as sulfanilic acid derivatives are known to be used for the above menacid and metanilic acid, toluidine sulfonic acids, chlorotioned purposes, however, being added to soap and aniline sulfonic acids, paminobenzoic acid, anthranylic synthetic washing agents, most of these compounds acid, N-methylaniline, N-ethylaniline and N-phenyl rather color the appearances of soaps and synthetic washethanolamine, and examples of alkoxy radicals include ing agents in pale yellow shade, and even effective comrnethoxy and ethoxy radicals.

The compounds used in the present invention and represented by the above general formula are very much superior to the corresponding anilino compounds, i.e., the compounds of both X and X in the above general formula are hydrogen atom, concerning the effects of improving the appearances of the soaps or synthetic washing agents. And in the present compounds, the compounds, the compounds having methyl radicals as X and X in the above general formula are rather superior to those having ethyl radicals as X and X in the above general formula concerning the improving effects of the appearances of the soaps or synthetic washing agents.

The appearances of the present soaps and synthetic washing agents are less changeable by the effects of external conditions, such as moisture, than those containing the corresponding anilino compounds. This is one of the characteristic properties of the present invention.

Further the present soaps and synthetic washing agents are considerably stabler than those containing conventional optical brightening agents, when they are used together with chloric bleaching agents in the washing of articles, and possess higher optical brightening action towards articles to be washed than those containing the corresponding anilino compounds. This is another characteristic property of the present invention.

The soaps include Marseille soap and the synthetic washing agents include those containing, as the essential component, alkylaryl sulfonate, e.g., sodium dodecylbenzene sulfonate, and higher alcohol surfuric acid esters, e.g., sodium oleyl sulfate, and being solid type.

The shape of the washing agent product according to the present invention includes blocks, flakes, beads and powders. Especially beads and powders are preferred.

The soaps and synthetic washing agents according to the present invention are prepared as follows.

A solution of a slurry of a soap, a synthetic washing agent or a mixture of them is added with at least one of 4,4-bis-triazinylaminostilbene-2,2'-disulfonic acid sodium salt of the present invention in the form of powder, solution or suspension in an amount of 0.01 to 1% by weight based upon the weight of the washing agent, mixed homogeneously and dried, and then crushed.

As to the content of the 4,4-bis-triazinylaminostilbene-2,2'-disulfonic acid sodium salt of the present invention, even 0.01% by weight of the compound based upon the weight of the washing agent may improve the whiteness of the appearance of the soaps and synthetic washing agents, and 1% or more than 1% by weight may be chosen, if desired and possible, depending upon the compounds and the purposes such as improving of the whiteness of the appearances of the soaps and synthetic Washing agents and increasing of the effect of brightening articles to be washed.

The compound used in the present invention may be admixed to the solution or slurry of a soap, a synthetic washing agent or a mixture of them itselfor to the solution or slurry of a soap, a synthetic washing agent or a mixture of them containing preferred builder such as sodium sulfate, phosphoric acid salts, sulfonic acid salts of benzene series sodium carbonate, CMC and the like. After the compound of the present invention is added to a solution or slurry of a soap, a synthetic washing agent or a mixture of them, powdery builders as mentioned above may be added thereto. After the admixing, the solution or slurry may be dried with hot air, or may be dried by using vacuum dryer at room temperature, spray-dryer or dropping method in vacuum.

The compounds of the present invention may be applied to the mixture of more than one kind of soaps or synthetic washing agents.

Further the compounds of the present invention can improve the appearances of soaps or synthetic washing agents colored by the addition of other known compounds, and can be applied together with known compounds thereby to suppress or neutralize the coloring of soaps or synthetic washing agents which will be caused by the addition of such known compounds.

The following examples are given in order to illustrate the present invention more concretely but the invention is not intended to be restricted to the examples.

The parts in the examples are by weight, unless otherwise indicated.

EXAMPLE 1 To a slurry obtained by mixing 100 parts of sodium dodecylbenzenesulfonate with 50 parts of water, a solution obtained by dissolving 1 part of sodium 4,4.-bis(2-N- methylanilino 4-monoisopropanolamino triazin 6 ylamino)stilbene-2,2-disulfonate in 10 parts of water with heating, was admixed and stirred to yield homogeneous slurry. The resulting slurry was dried with hot air at 60 C. and crushed, whereby the powdery washing agent, the appearance of which was much whiter than that of original material, was obtained.

EXAMPLE 2 To a solution of 100 parts of Marseille soap in 200 parts of water, a solution obtained by dissolving 0.3 parts of sodium 4,4 bis(2 N methylanilino-4-m-sulfoanilinotriazin 6 ylamino)stilbene-2,2'-disulfonate in 10 parts of water, was admixed and stirred. The resulting mixture was spray-dried, whereby a powdery soap, the appearance of which was whiter than the original soap, was obtained.

EXAMPLE 4 One hundred parts of Marseille soap Was mixed with 50 parts of water and heated to soften the soap.

One-hundredth part of sodium 4,4 bis(2 N-methylanilino 4 methoxy triazin 6 ylamino)stilbene-2,Z- disulfonate in powdery form was added thereto, and dissolved by mixing well. The mixture was dried with hot air at C. and crushed, whereby a powdery soap having high degree of whiteness was obtained.

EXAMPLE 5 To a slurry of parts of sodium oleyl sulfate in 30 parts of water, a hot solution obtained by dissolving 0.5 part of sodium 4,4 bis(2 N methylanilinot-monoethanolamino triazin 6 ylamino) stilbene-2,2'-disulfomate in 5 parts of water was added and mixed homogeneously. The resulting mixture was dried in vacuum at room temperature and crushed, whereby a powdery washing agent, the appearance of which was extremely improved, was obtained.

EXAMPLE 6 To a slurry obtained by mixing 100 parts of sodium oleyl sulfate, 200 parts 'of sodium sulfate, 50 parts of sodium pyrophosphateand 200 parts of water, a hot solution of 0.1 part of 4,4 bis(2 N methylanilino-4- morpholino triazin 6 ylamino) stilbene 2,2-disulfonate, 1 part of sodium p-toluenesulfonate in 5 parts of water, was added and mixed homogeneously. The resulting mixture was dried by dropping method in vacuum, whereby beads like powdery washing agent, the appearance of which was white in high degree, was obtained.

EXAMPLE 7 T o a slurry obtained by mixing 100 parts of sodium dodecylbenzenesulfonate, 30 parts of Marseille soap, 100 parts of sodium sulfate, 20 parts of sodium carbonate, 50 parts of sodium tripolyphosphate and 200 parts of water, a solution obtained by dissolving 1 part of sodium 4,4- bis(2 -N ethylanilino 4 methylethanolamino-triazin- 6-ylamino)stilbene-2,2-disulfonate and 20 parts of sodium benzenesulfonate in 50 parts of water with heating, was added and stirred homogeneously. The resulting mixture was spray-dried, whereby a powdery Washing agent, the appearance of which was extremely improved, was obtained.

' EXAMPLE 8 To a slurry obtained by mixing with heating 100 parts of sodium dodecylbenzenesulfonate and 30 parts of water, 0.2 part of 4,4 bis(2,4 bis N-methylanilino-triazin-6- ylamino)stilbene-2,2'-disulfonate in a powder form was added, homogeneously mixed and dried in vacuum. The dried product was crushed together with blending with 100 parts of sodium sulfate and 50 parts of sodium tripolyphosphate, whereby a powdery washing agent, the appearance of which is extremely improved, was obtained.

EXAMPLE 9 To a slurry obtained by mixing 100 parts of sodium dodecylbenzene sulfonate, 100 parts of sodium sulfate, 100 parts of sodium tripolyphosphate and 200 parts of water, a hot solution of 1 part of the compound, prepared from the mixture of 1 mol portion :of 4,4-diaminostylbene-2,2-disulfonic acid, 2 mole portions of cyanuric chloride, 2 mole portions of N-methylaniline, 1 mole portion of methyl ethanolamine and 1 mole portion of monoisopropanolamine, in 10 parts of water, was added, homogeneously mixed and spray-dried, whereby a powdery washing agent, the appearance of which was extremely improved, was obtained. Thus obtained washing agent was found to be improved as well as the washing agent obtained by employing the corresponding 4,4-bistriazinyl aminostylbene 2,2'-disulfonic acid derivatives obtained by synthesis without mixing the raw materials, i.e., that obtained by employing each 0.5 part of sodium 4,4 bis(2 N methylani'lino-44nethylethanolaminotriazin 6 ylamino) -stilbene-2,2-disulfon-ate and sodium 4,4 bis(2 N methylanilino-4-monoisopropanolaminotriazin-6-ylamino)stilbene-2,2-disulfonate respectively.

EXAMPLE 10 To a slurry obtained by mixing .100 parts of sodium dodecylbenzene sulfonate, 70 parts of sodium sulfate, 70 parts of sodium tripolyphosphate, 30 parts of sodium carbonate, 5 parts of CMC and 100 parts of water, a hot solution of 1 part of a compound, obtained by reacting -1 mole portion of 4,4-diaminostilbene-2,2'-disulfonic acid, 2 mole portions of cyanuric chloride, a mixture of 1 mole portion of N-methylaniline and 1 mole portion of N-ethylaniline and 2 mole portions of monoisopropanolamine, 5 parts of sodium p-toluenesulfonate and 10 parts of water, was added, mixed, and dried in vacuum, and then crushed, whereby a powdery washing agent, the appearance of which was very much improved, was obtained.

Thus obtained washing agent was found to be improved as well as the washing agent obtained by employing the corresponding 4,4 bis-triazinylaminostilbene-2,Z'-disulfonic acid derivatives obtained by synthesis without mixing the raw materials, i.e., that obtained by employing each 0.5 parts of sodium 4,4'-bis(2-N-methylanilino-4- monoisopropanolamino triazin 6-ylamino)stilbene-2,2- disulfonate, and sodium 4,4-bis(2-N-ethylanilino-4-monoisopropanolamino triazin 6 ylamino)stilbene 2,2- disulfonate respectively.

EXAMPLE 11 To a slurry obtained by mixing a washing agent consisting of 0.5 part of sodium 4,4-bis(2-anilino-4-aminotriazin-6-ylamino) stilbene-2,2'-disulfonate which is known compound and parts of sodium dodecylbenzenesulfonate, the appearance of which washing agent was pale yellow shade, and 50 parts of water, a solution of 0.2 part of sodium 4,4 bis(2 N methylanilino-4-aminotriazin-6-ylamino)-sti-lbene-2,2'-disulfonate in 10 parts of water was added, homogeneously mixed and spray-dried, whereby a powdery washing agent, the appearance of which was whiter than that of original synthetic washing agent which was before admixing sodium 4,4-bis(2- anilino 4 amino triazin 6 ylamino)-stilbene-'2,2'- disulfonate, was obtained.

EXAMPLE 12 A washing agent, which is referred to as A, which was obtained by admixing 0.2% by weight of sodium 4,4-bis (2 anilino-4-monoisopropanol-amino-triazin--ylamino)- stilbene-2,2'-disulfonate wit-h 99.8% by weight of sodium dodecylbenzenesulfonate which is known compound, was recognized to have improved whiteness in the appearance, however, a washing agent, which is referred to as B, which was obtained by admixing 0.2% by weight of the corresponding sodium 4,4-bis(Z-N-methylanilino-4-monoisopropanolamino triazin G-ylamino) stilbene-2,2'-disulfonate of the present invention with 99.8% by Weight of sodium dodecylbenzene-sulfonate was found to be far improved in the appearance with high degree of whiteness, as compared with A. When A was allowed to stand in air until the weight of A was increased by 5% by weight based on the weight of A by absorbing moisture, the whitening effect in the appearance was lost, while B was found to be stable and small in the decrease of degree of whiteness in the appearance, and as ever holding the very much improved appearance, after the same preservation condition as A.

EXAMPLE 13' A washing agent, which is referred to as C, which was obtained by admixing 0.2% by weight of sodium 4,4 bis(2 anilino 4-ethanolamino-triazin-6-ylamino) stilbene-2,2-disulfonate with 99.8% by weight of sodium dodecylbenzenesulfonate which is known compound, was found to be very much decreased in the optical brightening effect of articles to be washed, when employed in the washing bath containing 100-500 p.p.m. by weight of available chlorine based upon the weight of the washing bath, as compared with a washing agent, which is referred to as D, which was obtained by admixing 0.2% by weight of the corresponding sodium 4,4-bis(Z-N-methylanilino- 4-ethano'laminoetriazin=6-ylamino)stilbene disulfonate of the present invention with 99.8% by weight of sodium dodecylbenzenesulfonate.

D showed very much increased whiteness in the appearance, whereas C showed greenish yellow shade in the appearance, and the diiference of the appearance between C and D further increased conspicuously, by the effection of the external conditions.

What we claim is:

1. A composition consisting essentially of a member selected from the group consisting of marseille soap, dodecyl benzene sulfonate, a higher alcohol sulfate, or mixture thereof, and about 0.01 to 1% by weight, based on the weight of the composition, of a brightening agent, 4,4-bis-triazinylstilbene-2,2'-disulfonic acid derivative having the formula,

N l l 1 1 I l 2'1 som sOiM wherein X and X each represents methyl or ethyl radical; Y and Y each represents amino, cyclohexylamino, primary or secondary alkylamino having 1 to 4 carbon atoms, or primary or secondary hydroxyalkyl'amino, with each radical having 1 to 3 carbon atoms; and M represents hydrogen or alkali metal.

2. A composition according to claim 1 wherein the disulfonic acid derivative is sodium 4,4-bis(2-N-methylanilino 4 monoisopropanolamino triazine-6-ylamino) stilbene-2,2'-disulfonate.

3. A composition according to claim 1 wherein the disulfonic acid derivative is sodium 4,4-bis(2-N-methylanilino-4-methyl ethanolamino-triazin-6-ylamino stilbene- 2,2'-disulfonate.

4. A composition according to claim 1 wherein the disulfonic acid derivative is sodium 4,4'-bis(2-N-methyl- :anilino 4 monoethanolamino triazin 6 ylamino)stilbene-2,2'-disulfonate.

5. A composition according to claim 1 wherein the disulfonic acid derivative is sodium 4,4'-bis(2-N-ethylani- 1ino-4-methyl ethanolamino-triazin-6-ylamino)stilbene-2, 2-disulfonate.

6. A composition according to claim 1 wherein the disulfonic acid derivative is sodium 4,4'-bis(2,4-bis-N- methylanilino-triazin-6-ylamino)stilbene-2,2'-disulfonate.

7. A composition according to claim 1, wherein Y and Y each is a member selected from the group consisting of monomethylamino, monoethylamino, n-butylamino, dimethylamino, diethylamino and methylethylamino.

8. A composition according to claim 1, wherein Y and Y each is a member selected from the group consisting of monoethanol amino, monoisopropanolamino, diethanolamino, methylethanolamino, ethyl ethanolamino and diisopropanolamino. .7

9. A composition according to claim 1, further consisting essentially of an effective amount of at least one builder selected from the group consisting of sodium sulfate, sodium tripolyphosphate sodium pyrophosphate, and sodium carbonate. I :5,

10. A composition according to claim 9 further consisting essentially of an eifective amount of sodiump-toluene sulfonate as a builder. I

11. A composition according to claim 9 further consisting essentially of an elfective amount of carboxy methyl cellulose as a builder.

References Cited UNITED STATES PATENTS- FOREIGN PATENTS 224,118 11/1962 Austria. 941,993 11/1963 Great Britain. 930,393 7/1963 Great Britain.

OTHER REFERENCES Chemical Abstracts, volume 60, column 4289.

LEON D. ROSDOL, Primary Examiner.

O s. D. SCHWARTZ, Examiner.

S. E. DARDEN, Assistant Examiner. 

1. A COMPOSITION CONSISTING ESSENTIALLY OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF MARSEILLE SOAP, DODECYL BENZENE SULFONATE, A HIGHER ALCOHOL SULFATE, OR MIXTURE THEREOF, AND ABOUT 0.01 TO 1% BY WEIGHT, BASED ON THE WEIGHT OF THE COMPOSITION, OF A BRIGHTENING AGENT, 4,4''-BIS-TRIAZINYLSTILBENE-2,2''-DISULFONIC ACID DERIVATIVE HAVING THE FORMULA, 